Laminates of glass or metal and poly(alkylene dicarboxylates) and syntheses thereof

ABSTRACT

Poly(alkylene dicarboxylate) polymers and copolymers having tetraalkyl- or trialkylammonium ion end groups and methods of synthesis, thereof. The methylene-containing copolymers, in general, adhere to glass and metals, including aluminum, iron, and copper. Poly(methylene-co-ethylene terephthalate) is a clear film useful in the protection of metals or glass from corrosion or scratching. Glass may be bound to glass or to metal using the polymers of the present invention or metal to metal seals may be made.

This application is a divisional of U.S. Ser. No. 08/929,969 filed Sep.15, 1997 now U.S. Pat. No. 5,837,381 which is a divisional applicationof U.S. Ser. No. 08/123,368 filed Sep. 17, 1993 now U.S. Pat. No.5,451,643 which is a divisional application of Ser. No. 08/027,134 filedMar. 5, 1993 now U.S. Pat. No. 5,371,171.

BACKGROUND OF THE INVENTION

Polyoxalates have been previously prepared by ester interchange withdiols such as ethylene glycol, 1,3-propanediol, or 1,4-butanediol withdiethyloxalate [Carothers et al., J. Am. Chem. Soc., 52, 3292 (1930);Gordon et al., Polym. Prepr. (Am. Chem. Soc., Div. Polym. Chem.)31, 507(1990); Thibeault et al., J. Polym. Sci., Pt. A: Polym. Chem., 28, 1361(1990); Shalaby et al., U.S. Pat. No. 4,141,087 (1979)], by reactions ofoxalic acid with alkylene glycols [Ellis, U.S. Pat. No. 2,111,762(1938)], and by condensations of diols with oxaloyl chloride [Piraner etal., Makromol. Chem., 193, 681 (1992)]. Linear polyesters have also beenprepared by reactions of dicarboxylic acids and diols [Carothers, U.S.Pat. Nos. 2,071,250 and 2,071,251].

Poly(methylene sebacate) was synthesized via a reaction of cesiumsebacate with bromochloromethane (Cimecioglu et al., Journal of PolymerScience: Part A: Polymer Chemistry, 30:313-321 (1992); Cimecioglu, A. L.and G. C. East, Makromol. Chem. Rapid Commun., 1989, 10:319), similarly,poly(methylene terephthalate) was synthesized via a reaction of cesiumor potassium terephthalate with dibromomethane or bromochloromethane(Cimecioglu et al., Journal of Polymer Science: Part A: PolymerChemistry 26:2129-2139 (1988)). The highest M_(n) reported by A. L.Cicecioglu and G. C. East, (J. Polym. Sci., Pt. A: Polym Chem., 1992,30:313) was 42,300; their polymers were prepared by reaction of cesiumterephthalate with bromochloromethane in N-methylpyrrolidone. East andMorshed (Polymer, (1982) vol. 23:168-170 and 1555-1557) haveaccomplished the synthesis of poly(methylene esters). Poly(methyleneterephthalate) is listed as one of the base layers of a film forcassette-type magnetic tape, however, no reference to a preparation wasmade. (Shiba, H., DE 3,306,089, Sep. 1, 1983; JP Appl. 82/ut24503, Feb.23, 1982; Chem. Abst., 1983, 99, 213807).

Poly(ethylene terephthalate) (PET) is a commercially important polyesterhaving many applications. PET is known under trade names Dacron®(DuPont), Mylar® film, Kodel® (Eastman Kodak) and Terylene® (Terene). Ofseveral methods of preparation, the most common is the catalyzed esterinterchange between dimethyl terephthalate and ethylene glycol involvingremoval of methanol to drive the reaction to completion. Poly(ethyleneterephthalate) was reportedly prepared by reaction with cesiumterephthalate; however, no details are given and the other reactant wasnot mentioned (G. C. East and M. Morshed, Polymer, 1982, 23:168). Acommercial sample of poly(ethylene terephthalate) had M_(n) =3,600.Poly(ethylene isophthalate) has been previously synthesized byNishikubo, T. and K. Ozaki (Polym. J. 1990, 22:1043).

Poly(p-xylene terephthalate) was previously prepared by the followingmethod: Reaction of sodium or potassium terephthalates with p-xylylenedichloride or dibromide in the presence of crown ethers (15-crown-S or18-crown-6). Low yields and low molecular weights were reported. [G.Rokicki, J. Kielkiewicz, and B. Marciniak, Polimery (Warsaw), 1982,27:374; Chem. Abst., 1982, 99:38837].

Poly(m-xylene terephthalate) was reportedly synthesized by reaction ofisophthalic acid, 1,8-diazabicyclo-[5.4.0]-7-undecene, and m-xylylenedibromide in dimethylformamide or dimethylsulfoxide. (T. Nishikubo andK. Ozaki, Polym. J., 1990, 22:1043). The polymer was reported to havemoderate viscosity (0.19 dlg⁻¹).

Bis (tetrabutylammonium) terephthalate was reported as a component incrosslinked vinyl chloride resin foam compositions (Otsuka Chemical Co.,Ltd., Jpn. Pat. 582154430, December 1983; Chem. Abst., 1984,100:175926). IR and Raman spectra have been reported for bis(tetraethylammonium) terephthalate (Makarevich, N. I., and Sushko, N.I., Zh. Prikl. Specktrosk., 1989, 50:65; Chem. Abst., 1989, 110:201792).

Ever since health concerns about asbestos began to surface, producershave been driven to develop suitable alternatives. Traditionally,asbestos has been woven into cloths and garments, compressed intoboards, gaskets, and pipe coverings, and used as a filler andreinforcement in paint, asphalt, cement and plastic. To date, no singleproduct has emerged that is as inexpensive, inert, strong orincombustible as asbestos.

The poly(methylene oxalate) (PMO) {systematic name:poly[oxy(1,2-dioxo-1,2-ethanediyl) oxymethylene]}, of the presentinvention cannot be prepared by any of the methods described abovebecause the glycol that would be needed (HOCH₂ OH) is not stable undernormal conditions but decomposes into formaldehyde and water.Poly(methylene oxalate) has unusual properties useful, for example, inthe formulation of objects which are non-flammable and resistant to hightemperatures and action of organic solvents.

Based on the synthesis of poly(methylene oxalate), a new synthesis ofpoly(alkylene dicarboxylates) and copolymers of poly(alkylenedicarboxylates) is provided by the present invention. New copolymers areprovided, in particular, methylene copolymers, as well as polymers withnew end groups. The methods of the present invention allow the synthesisof polymers and copolymers having molecular weights higher thanpreviously described.

ABBREVIATIONS

DP=Degree of polymerization

M=Number average molecular weight

DSC=Differential scanning calorimetry

SUMMARY OF THE INVENTION

The present invention provides a polymer having the structure ##STR1## Xis a tetraalkyl- or a trialkylammonium ion, R is aliphatic or aromaticand n is a number of repeating units. The present invention alsoprovides a polymer having the structure ##STR2## X is a tetraalkyl- ortrialkylammonium ion, R' and R" are independently aryl, alkyl orarylalkyl, m and m' are independently 1 or 2, p, q and n are a number ofrepeating units. The values of p and q will depend upon the ratio ofstarting materials. In the above polymers, the tetraalkylammonium ionmay be Bu₄ N⁺, Et₄ N⁺ or R'Me₃ N⁺, where R' is benzyl or an alkyl largerthan butyl. A preferred alkyl is hexadecyl. A preferred trialkylammoniumion is Et₃ HN⁺.

The polymer structures of the present invention include a poly(alkylene) dicarboxylate having a tetraalkyl- or trialkylammonium endgroup. The alkylene may be methylene, ethylene, p-xylene, m-xylene or2-E-butene. The dicarboxylate may be terephthalate, sebacate,isophthalate, succinate, or adipate. The tetraalkylammonium end groupmay be Bu₄ N⁺, Et₄ N⁺ or R'Me₃ N⁺, where R' is benzyl or an alkyl largerthan butyl. The trialkylammonium end group may be Et₃ HN⁺.

A further embodiment of the present invention is a poly (alkyleneldicarboxylatel-co-alkylene2 dicarboxylate2) having a tetraalkyl- ortrialkylammonium end group. The alkylenel may be methylene, and thealkylene2 may be ethylene, 2-E-butene or p-xylene. The dicarboxylatelmay be terephthalate or oxalate, and the dicarboxylate2 may beterephthalate or oxalate, the tetraalkylammonium end group may be Bu₄N⁺, Et4N⁺ or R'Me₃ N⁺, where R' is benzyl or an alkyl larger than butyl,and the trialkylammonium end group may be Et₃ HN⁺.

Further compositions of the present invention include poly(methyleneterephthalate-co-ethylene terephthalate), poly(methyleneoxalate-co-ethylene oxalate), poly(m-xylene terephthalate) having endgroups X, where X is a tetraalkyl- or a trialkylammonium ion,poly(methylene terephthalate-co-2-butenyl terephthalate), poly(methyleneterephthalate-co-p-xylene terephthalate), bis(benzyltrimethylammonium)terephthalate, and bis(tetrabutylammonium) sebacate. These polymers mayhave end groups X, where X is a tetraalkyl- or a trialkylammonium ion.The tetraalkylammonium ion may be Bu₄ N⁺, Et₄ N⁺ or R'Me₃ N⁺, where R'is benzyl or an alkyl larger than butyl, and the trialkylammonium ionmay be Et₃ HN⁺.

The present invention provides a first method for preparing apoly(alkylene dicarboxylate) using a tetraalkyl salt. The methodcomprises the step of reacting a bis(R¹ R² R³ R⁴ ammonium) dicarboxylatewith alkylene chloride, alkylene bromide, alkylene iodide orbromochloroalkane in a mutual solvent. R¹, R², R³ and R⁴ are alkyl orarylalkyl and R¹, R², R³ and R⁴ are not all methyl. The method isdefined further as including the steps of collecting the poly(alkylenedicarboxylate); and removing unreacted reagents. The bromochloroalkanemay be bromochloromethane or bromochloroethane. The dicarboxylate may beterephthalate or sebacate.

The present invention provides a second method for preparing apoly(alkylene dicarboxylate) using a trialkyl salt. The method comprisesthe steps of forming a bis(trialkylammonium) dicarboxylate salt, andreacting the bis(trialkylammonium) dicarboxylate salt with alkylenechloride, alkylene bromide or alkylene iodide. The dicarboxylate may beterephthalate or isophthalate.

A further embodiment of the present invention is a method for preparinga poly(alkylenel-co-alkylene2 dicarboxylate) copolymer. The methodincludes the step of reacting bis(R¹ R² R³ R⁴ ammonium) dicarboxylatewith a mixture of alkylenel bromide and alkylene2 bromide in a mutualsolvent. R¹, R², R³ and R⁴ may be alkyl or arylalkyl and R¹, R², R³ andR⁴ may not be all methyl. The method is defined further as including thesteps of collecting the copolymer, and removing unreacted reagents. Theratio of alkylenel bromide to alkylene2 bromide may be other than one toone. The alkylene2 may be ethylene, p-xylene or 2-butene and thealkylene2 bromide may be ethylene bromide, 1,2 dibromoethane, 1,4dibromo-2-butene or α,α'-bromo-p-xylene. The dicarboxylate may have thestructure R(CO₂ ⁻)₂ where R is aryl or vinyl or the dicarboxylate may beterephthalate or oxalate.

A second method for preparing a poly(alkylenel-co-alkylene2dicarboxylate) includes the use of a trialkyl salt. The method comprisesthe steps of forming a bis(trialkylammonium) dicarboxylate salt, andreacting the bis(trialkylammonium) dicarboxylate salt with a mixture ofalkylenel halide and alkylene2 halide. The alkylenel halide and thealkylene2 halide may be present in a ratio other than one to one. Thealkylene2 may be ethylene and the halide may be bromide, chloride oriodide.

The present invention also provides a method for preparing a poly(R'dicarboxylate). The method comprises the step of reacting a bis(R¹ R² R³R⁴ ammonium) dicarboxylate with a dihalide, X--R'--X in a mutualsolvent. R¹, R², R³ and R⁴ may be alkyl or arylalkyl and R¹, R², R³ andR⁴ may not be all methyl, X may be bromide, chloride or iodide, and R'may be --CH₂ --Ar--CH₂ -- or --CH₂ CH═CHCH₂ -- where Ar is aromatic,such as 1,4- or 1,3-C₆ H₄, for example. R' may be 2-E-butene andX--R'--X may be 1,4 dibromo-2-E-butene.

A second method for preparing a poly(R' dicarboxylate) comprises the useof a trialkyl salt. The method includes the steps of forming abis(trialkylammonium) dicarboxylate salt; and reacting thebis(trialkylammonium) dicarboxylate salt with α,α'-dibromo-R' orα,α'-dichloro-R'. R' may be p-xylene, m-xylene or 2-E-butene.

The present invention also provides a method for preparing abis(tetraalkylammonium) dicarboxylate salt. The method includes the stepof reacting a dicarboxylic acid with tetraalkyl ammonium hydroxide. Thedicarboxylic acid may be terephthalic acid or sebacic acid. Thetetraalkyl ammonium hydroxide may be tetrabutyl-, tetraethyl- orbenzyltrimethylammonium hydroxide. In each of the above methods, R¹, R²,R³ and R⁴ may be ethyl or butyl or R¹, R², and R³ may be methyl and R⁴may be benzyl or an alkyl larger than butyl. A preferred alkyl ishexadecyl. The alkylene may be methylene or ethylene, the alkylenel maybe methylene, and the bis(trialkylammonium) may bebis(triethylammonium). The dicarboxylate may be terephthalate.

The present invention further provides for multilayered structurescomprising a poly(methylene dicarboxylatel-coalkylene dicarboxylate2)copolymer layer with a first and second side and a metal or glass layeradherent to one or both sides. The particular copolymers employed arethose which exhibit adhesive interactions with at least one of metal andglass. Such adhesive interactions are readily identified by simplyapplying a subject copolymer in a liquid form to a metal or glasssurface and observing it, upon conversion to a solid state, if there isnoticeable significant adhesion between the polymer and the surface.

In a preferred embodiment a metal layer or structure may be protected byformation of a copolymer layer thereupon. This copolymer layer, inaddition to potentially being a protective layer for the metal surface,may also form the basis for the addition of a second layer of metal orglass, the adherence being mediated by the adherent copolymer of thepresent invention when the second layer is contacted with the stillliquid copolymer.

The adherency of the dicarboxylatel-co-alkylene dicarboxylate2 copolymerto metal or glass may be modified by the particular dicarboxylatesutilized and the proportion of the particular alkylene substituents. Inone preferred embodiment, the alkylene substituent must be greater than12% methylene. Again, the adherency of the subject copolymers may besimply tested and determined by only reasonable experimentation.

In certain cases, the particular copolymer utilized may be one whichretains maleability at ambient temperatures. This maleability willserve, for example, to prepare glass-copolymer-glass multilayeredstructures akin to safety glass commonly utilized.

Preferred dicarboxylate functions are terephthalates although others mayperform likewise and are readily tested. The alkylenes utilized incopolymer formation are preferably ethylene, p-xylene or but-2-ene, inaddition of course to methylene.

The present invention includes a method of preparing multilayeredstructures with a poly(methylene dicarboxylate1-co-alkylenedicarboxylate2) copolymer layer having adhesion for glass or metalsurfaces and having a glass or metal layer adherent to both sides. Themethod comprises first providing at least two metal or glass layers,each layer having at least one surface. Next, a poly(methylenedicarboxylatel-co-alkylene dicarboxylate2) copolymer having adhesivecharacter for metal or glass is converted to a liquid state, preferablyby melting. At least one of the metal or glass surfaces is then coatedwith the molten copolymer. Then a coated surface is contacted withanother coated surface or an uncoated surface of metal or glass to forma multilayered structure. Various metals may be utilized in theformation of such multilayered structures, including aluminum, iron andcopper. For the particular copolymers, dicarboxylatel may be the same ordifferent from dicarboxylate2.

Another aspect of the present invention is a method of using apoly(alkylenel dicarboxylatel-co-alkylene2 dicarboxylate2) copolymer asan agent for protecting a surface from corrosion or scratching. Themethod comprises the steps of melting the poly(alkyleneldicarboxylatel-co-alkylene2 dicarboxylate2) copolymer to form a moltencopolymer and coating the surface with the molten copolymer to form acopolymer-coated surface.

The methods of the present invention allow the synthesis and use ofpolymers and copolymers having molecular weights higher than thosepreviously described. The synthesis does not use cesium, instead, thesynthesis uses a tetraalkyl salt as an intermediate in the synthesis ofthe polymers and copolymers.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows the infrared spectrum of poly(methylene oxalate) using KBrpressed pellet: cm⁻¹ %; 2981 62.11, 2922 58.26, 1657 00.33, 1325 2.01,1098 33.50, 934.5 28.61.

FIG. 2 shows the infrared spectrum of bis(tetrabutylammonium) oxalateobtained in CDCl₃ using a NaCl salt plate: cm-1%; 2932.2 87.84, 1641.023.72, 1325.3 40.53, 914.7 88.54, 833.9 83.00, 779.4 58.85, 744.8 87.65.

FIG. 3 shows the ¹ H NMR spectrum of bis(tetrabutylammonium) oxalate inCDCl₃.

FIG. 4 shows the ¹³ C NMR spectrum of bis(tetrabutylammonium) oxalate inCDCl₃.

FIGS. 5A, 5B and 5C show the structures of novel polymers of the presentinvention or polymers synthesized by novel methods of the presentinvention.

FIG. 5A shows:

a is Poly(methylene oxalate),

b is Poly(methylene oxalate-co-ethylene oxalate),

c is Poly(ethylene terephthalate),

d is Poly(methylene terephthalate),

e is Poly(methylene isophthalate), and

f is Poly(ethylene isophthalate).

FIG. 5B shows:

g is Poly(methylene terephthalate-co-ethylene terephthalate),

h is Poly(p-xylene terephthalate),

i is Poly(m-xylene terephthalate), and

j is Poly(methylene terephthalate-co-p-xylene terephthalate).

FIG. 5C shows:

k is Poly(2-E-butenyl terephthalate),

l is Poly(methylene terephthalate-co-2-E-butenyl terephthalate),

m is Poly(methylene sebacate), and

n is Poly (methylene sebacate-co-ethylene sebacate).

FIG. 6 show a ¹ H NMR spectrum in CDCl₃ /TFAD mixture of poly(methyleneterephthalate) obtained by the reaction of methylene bromide withterephthalic acid and triethylamine in DMF.

FIG. 7 shows a ¹³ C NMR spectrum in CDCl₃ /TFAD mixture ofpoly(methylene terephthalate) obtained by the reaction of methylenebromide with terephthalic acid and triethylamine in DMF.

FIG. 8 shows a ¹ H NMR spectrum in CDCl₃ /TFAD mixture of poly(methyleneterephthalate) obtained by the reaction of methylene bromide andbis(tetrabutylammonium) terephthalate in chlorobenzene.

FIG. 9 shows a ¹³ C NMR spectrum in CDCl₃ /TFAD mixture ofpoly(methylene terephthalate) obtained by the reaction of methylenebromide and bis(tetrabutylammonium) terephthalate in chlorobenzene.

FIG. 10 shows a ¹ H NMR spectrum in CDCl₃ /TFAD mixture ofpoly(methylene terephthalate) obtained by the reaction of methylenechloride and bis(tetrabutylammonium) terephthalate in DMF.

FIG. 11 shows a ¹ H NMR spectrum in CDCl₃ /TFAD mixture ofpoly(methylene terephthalate) obtained by the reaction of methylenechloride and bis(tetraethylammonium) terephthalate in DMF.

FIG. 12 shows a ¹³ C NMR spectrum in CDCl₃ /TFAD mixture ofpoly(methylene terephthalate) obtained by the reaction of methylenechloride and bis(tetraethylammonium) terephthalate in DMF.

FIG. 13 shows a ¹ H NMR spectrum in CDCl₃ of poly(methylene sebacate)obtained by the reaction of bis(tetrabutylammonium) sebacate withmethylene bromide.

FIG. 14 shoes a ¹³ C NMR spectrum in CDCl₃ of poly(methylene sebacate)obtained by the reaction of bis(tetrabutylammonium) sebacate withmethylene bromide.

FIG. 15 shows a ¹ H NMR spectrum in CDCl₃ /TFAD mixture of poly(ethyleneterephthalate) obtained by the reaction of ethylene bromide withterephthalic acid and triethylamine in DMF.

FIG. 16 shows a ¹³ C NMR spectrum in CDCl₃ /TFAD mixture ofpoly(ethylene terephthalate) obtained by the reaction of ethylenebromide with terephthalic acid and triethylamine in DMF.

FIG. 17 shows a ¹ H NMR spectrum in CDCl₃ /TFAD mixture of poly(ethyleneterephthalate) obtained by the reaction of ethylene bromide andbis(tetraethylammonium) terephthalate in DMF.

FIG. 18 shows a ¹³ C NMR spectrum in CDCl₃ /TFAD mixture ofpoly(ethylene terephthalate) obtained by the reaction of ethylenebromide and bis(tetraethylammonium) terephthalate in DMF.

FIG. 19 shows a ¹ H NMR spectrum in CDCl₃ /TFAD mixture of poly(ethyleneisophthalate) obtained by the reaction of ethylene chloride withisophthalic acid and triethylamine in DMF.

FIG. 20 shows a ¹³ C NMR spectrum in CDCl₃ /TFAD mixture ofpoly(ethylene isophthalate) obtained by the reaction of ethylenechloride with isophthalic acid and triethylamine in DMF.

FIG. 21 shows a ¹ H NMR spectrum in CDCl₃ /TFAD mixture ofpoly(methylene-co-ethylene terephthalate) (1:1 mole ratio added; 43:57incorporation) obtained by the reaction of methylene bromide andethylene bromide with bis(tetrabutylammonium terephthalate) inchlorobenzene.

FIG. 22 shows a ¹³ C NMR spectrum in CDCl₃ /TFAD mixture ofpoly(methylene-co-ethylene terephthalate) (1:1 mole ratio added; 43:57incorporation) obtained by the reaction of methylene bromide andethylene bromide with bis(tetrabutylammonium terephthalate) inchlorobenzene.

FIG. 23 shows a ¹ H NMR spectrum in CDCl₃ /TFAD mixture ofpoly(methylene-co-ethylene terephthalate) (63:37 mole ratio added; 21:79incorporation) obtained by the reaction of methylene bromide andethylene bromide with bis(benzyltrimethylammonium terephthalate) inchlorobenzene.

FIG. 24 shows a ¹ H NMR spectrum in CDCl₃ /TFAD mixture ofpoly(methylene-co-ethylene terephthalate) (17:83 mole ratio added; 12:88incorporation) obtained by the reaction of methylene bromide andethylene bromide with bis(tetrabutylammonium terephthalate) inchlorobenzene.

FIG. 25 shows a ¹³ C NMR spectrum in CDCl₃ /TFAD mixture ofpoly(methylene-co-ethylene terephthalate) (17:83 mole ratio added; 12:88incorporation) obtained by the reaction of methylene bromide andethylene bromide with bis(tetrabutylammonium terephthalate) inchlorobenzene.

FIG. 26 shows a ¹ H NMR spectrum in CDCl₃ /TFAD mixture ofpoly(methylene-co-ethylene terephthalate) (1:1 mole ratio added; 36:64incorporation) obtained by the reaction of ethylene chloride withterephthalic acid and triethylamine in DMF.

FIG. 27 shows a ¹³ C NMR spectrum in CDCl₃ /TFAD mixture ofpoly(methylene-co-ethylene terephthalate) (1:1 mole ratio added; 36:64incorporation) obtained by the reaction of ethylene chloride withterephthalic acid and triethylamine in DMF.

FIG. 28 shows an IR spectrum by KBr pressed pellet of poly(methyleneoxalate-co-ethylene oxalate) obtained by the reaction of methylenebromide and ethylene bromide (1:1 mole ratio) withbis(tetrabutylammonium oxalate) in chlorobenzene.

FIG. 29 shows a ¹ H NMR spectrum in CDCl₃ /TFAD mixture of poly(p-xyleneterephthalate) obtained by the reaction of α,α'-dibromo-p-xylene withterephthalic acid and triethylamine in DMF.

FIG. 30 shows a ¹³ C NMR spectrum in CDCl₃ /TFAD mixture ofpoly(p-xylene terephthalate) obtained by the reaction ofα,α'-dibromo-p-xylene with terephthalic acid and triethylamine in DMF.

FIG. 31 shows a ¹ H NMR spectrum in CDCl₃ of poly(m-xyleneterephthalate) obtained by the reaction of α,α'-dichloro-m-xylene withbis(tetraethylammonium)terephthalate in DMF.

FIG. 32 shows a ¹³ C NMR spectrum in CDCl₃ of poly(m-xyleneterephthalate) obtained by the reaction of α,α'-dichloro-m-xylene withbis(tetraethylammonium)terephthalate in DMF.

FIG. 33 shows a ¹ H NMR spectrum in CDCl₃ /TFAD mixture ofpoly(2-butenyl terephthalate) obtained by the reaction of1,4-dibromo-2-butene with bis(tetraethylamonium terephthalate) in DMF.

FIG. 34 shows a ¹³ C NMR spectrum in CDCl₃ /TFAD mixture ofpoly(2-butenyl terephthalate) obtained by the reaction of1,4-dibromo-2-butene with bis(tetraethylamonium terephthalate) in DMF.

FIG. 35 shows a ¹ H NMR spectrum in CDCl₃ /TFAD mixture ofpoly(2-butenyl terephthalate) obtained by the reaction of1,4-dibromo-2-butene and terephthalic acid with triethylamine in DMF.

FIG. 36 shows a ¹³ C NMR spectrum in CDCl₃ /TFAD mixture ofpoly(2-butenyl terephthalate) obtained by the reaction of1,4-dibromo-2-butene and terephthalic acid with triethylamine in DMF.

FIG. 37 shows a ¹ H NMR spectrum in CDCl₃ /TFAD mixture ofpoly(methylene-co-p-xylene terephthalate) (50:50 mole ratio added; 48:52incorporation) obtained by the reaction of methylene bromide andα,α'-dibromo-p-xylene with bis(tetraethylammonium terephthalate) in DMF.

FIG. 38 shows a ¹³ C NMR spectrum in CDCl₃ /TFAD mixture ofpoly(methylene-co-p-xylene terephthalate) (50:50 mole ratio added; 48:52incorporation) obtained by the reaction of methylene bromide andα,α'-dibromo-p-xylene with bis(tetraethylammonium terephthalate) in DMF.

FIG. 39 shows a ¹ H NMR spectrum in CDCl₃ /TFAD mixture ofpoly(methylene-co-2-butenyl terephthalate) (53:47 mole ratio added;60:40 incorporation) obtained by the reaction of methylene bromide andDibromo-2-butene with bis(tetraethylammonium terephthalate) in DMF.

FIG. 40 shows a ¹³ C NMR spectrum in CDCl₃ /TFAD mixture ofpoly(methylene-co-2-butenyl terephthalate) (53:47 mole ratio added;60:40 incorporation) obtained by the reaction of methylene bromide anddibromo-2-butene with bis(tetraethylammonium terephthalate) in DMF.

FIG. 41 shows a ¹ H NR spectrum in CDCl₃ of bis(tetrabutylammonium)terephthalate obtained by the reaction of terephthalic acid withtetrabutylammonium hydroxide.

FIG. 42 shows a ¹³ C NMR spectrum in CDCl₃ of bis(tetrabutylammonium)terephthalate obtained by the reaction of terephthalic acid withtetrabutylammonium hydroxide.

FIG. 43 shows a ¹ H NMR spectrum in DMSO-d₆ of bis(tetraethylammonium)terephthalate obtained by the reaction of terephthalic acid withtetraethylammonium hydroxide.

FIG. 44 shows a ¹³ C NMR spectrum in DMSO-d₆ of bis(tetraethylammonium)terephthalate obtained by the reaction of terephthalic acid withtetraethylammonium hydroxide.

FIG. 45 shows a ¹ H NMR spectrum in CDCl₃ of bis(tetrabutylammonium)sebacate obtained by the reaction of sebacic acid withtetrabutylammonium hydroxide.

FIG. 46 shows a ¹³ C NMR spectrum in CDCl₃ of bis(tetrabutylammonium)sebacate obtained by the reaction of sebacic acid withtetrabutylammonium hydroxide.

FIG. 47 shows a ¹ H NMR spectrum in D₂ O of bis(benzyltrimethylammonium)terephthalate obtained by the reaction of terephthalic acid withbenzyltrimethylammonium hydroxide.

FIG. 48 shows a ¹³ C NMR spectrum in D₂ O ofbis(benzyltrimethylammonium) terephthalate obtained by the reaction ofterephthalic acid with benzyltrimethylammonium hydroxide.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

Poly(methylene oxalate) {systematic name:poly[oxy(1,2-dioxo-1,2-ethanediyl)oxymethylene]} has been synthesized.This polymer has unique properties which make it suitable for variousapplications. It is insoluble in all tested common organic solvents,does not melt, nonflammable, and is resistant to fire. The proof ofstructure of the material is from its infrared spectrum which showscarbonyl, carbon-oxygen single bond, and carbon-hydrogen stretchingbands in predicted positions (see FIG. 1).

Possible applications are-as a light-weight material for use at hightemperatures (for example, as a structural material in aircraft andspace vehicles, as a binder for brake systems, and an insulator formicroelectronic components); as a material for incorporation intoobjects to enhance their fire-resistance (for example, into plasticsused for making furniture); as an asbestos substitute and as a materialfrom which to make objects which will not dissolve in various solvents(for industrial uses). It may also be used as a heat-resistant coating,one example being for nose cones employed for space reentry vehicles.

Under a nitrogen atmosphere, poly(methylene oxalate) (PMO) does notbegin to decompose until the temperature reaches about 430° C. Onheating with a Bunsen burner flame, it sinters but does not burn. Thissintering or fusing together at high temperatures forms PMO fibersuseful in the aforedescribed applications.

PMO hydrolyzes slowly on stirring with sodium hydroxide solution for aperiod of several hours. For example, by placing PMO overnight in about15% NaOH, it will go into solution. Poly(methylene oxalate) is alsounusual in that it contains a very high percentage of oxygen (nearly63%) and yet is very stable.

The overall synthesis of PMO consists of several steps:

(1) conversion of oxalic acid into a bis(tetraalkylammonium) salt;

(2) removal of water and solvent;

(3) reaction of the salt with a methylene halide dissolved inappropriate solvents; and

(4) separation of byproduct tetra-alkylammonium halide from the polymer.

Thus, oxalic acid is reacted with two equivalents of atetra-alkylammonium hydroxide to form the salt in solution and thesolvent and water are removed to form the anhydrous oxalate salt:

    2[R.sub.4 N.sup.+ OH.sup.- ]+HOOC--COOH→R.sub.4 N.sup.+- OOC--COO.sup.-+ NR.sub.4 +2H.sub.2 O

The anhydrous salt is then heated in a solvent with the methylenehalide:

    (R.sub.4 N.sup.+).sub.2 C.sub.2 O.sub.4.sup.2- +CH.sub.2 X.sub.2 →R.sub.4 N.sup.+ (.sup.- OCOCOOCH.sub.2).sub.n OCOCOO.sup.-+ NR.sub.4 +R.sub.4 N.sup.+ X.sup.-

The precipitated polymer is separated from the solvent, for example, bycentrifugation or filtration and residual tetra-alkylammonium halide isseparated from poly(methylene oxalate) by washing the precipitate withmethanol. The tetra-alkylammonium halide is recovered by removal ofsolvents.

Preparation of Bis(tetrabutylAmmonium) Oxalate

Tetrabutylammonium hydroxide in methanol (90 mL of a 1 molar solution,0.098 mol) was added dropwise to 3.5 g (0.039 mol) of anhydrous oxalicacid under an argon atmosphere. The end-point was determined bytitration. The solvent was removed in vacuo and the residue was dried invacuo at 40° C. for 4 h and then at 60° C. for 9.5 h. A yield of 21 g ofproduct was obtained. The product was characterized asbis(tetrabutylammonium) oxalate by means of its ¹ H and ¹³ C NMR and IRspectra (FIGS. 2-4). Manipulations with bis(tetrabutylammonium) oxalatewere carried out in a dry glove-box in inert atmospheres (nitrogen orargon) since the compound is very hygroscopic. Bis(tetrabutylammonium)oxalate is a new composition of matter as well as are most of the otherbis(tetraalkylammonium) oxalates, an exception being tetraethylammoniumoxalate. Other tetraalkylammonium oxalates may be analogously used inplace of tetrabutylammonium oxalate to prepare PMO. Such compounds mayalso be used as substrates or inhibitors of oxalate metabolizingenzymes.

Preparation of Poly(methylene oxalate) (PMO) Using Methylene Bromide orMethylene Chloride

Bis(tetrabutylammonium) oxalate (12 g; 0.021 mol) was dissolved in 25 mLof chlorobenzene and methylene bromide (2.6 mL; 4.0 g; 0.023 mol) wasadded. Other solvents such as nitrobenzene, bromobenzene, andN-methylpyrrolidone, for example, may be used in place of chlorobenzene.The solution was heated at reflux for about 6.3 h and allowed to cool toroom temperature. A white precipitate formed and was isolated bycentrifugation. It was then washed three times with 50 Ml portions ofmethanol to remove tetrabutylammonium bromide and unreacted startingmaterials, and dried in vacuo for about 2 days. The poly(methyleneoxalate) product weighed 0.29 g. PMO is not soluble in any of the commonorganic solvents, however, it dissolved in concentrated sulfuric acid. A¹³ C NMR spectrum of the acid solution showed carbonyl and methylenecarbon signals at lower and higher field positions, respectively. Thepolymer did not reprecipitate when the sulfuric acid solution was pouredinto cold water. An infrared spectrum with a sample of the polymer in apressed KBr pellet showed absorption peaks for C--H, C═O, and C--Ostretching and C--H bending vibrations (FIG. 1). In a differentialscanning calorimeter (DSC), PMO did not melt on heating to about 410°C., at which temperature it began to decompose.

Byproduct tetrabutylammonium bromide (12 g) was recovered from the abovefiltrate (from PMO) by evaporation of chlorobenzene and methanolsolvents. A ¹ H NMR spectrum on the compound in CDCl₃ showed theexpected four groups of peaks for the butyl group. Tetrabutylammoniumbromide can be recycled back into tetrabutylammonium hydroxide bypassage through an anionic exchange column to exchange hydroxide for thebromide ion or directly into bis(tetrabutylammonium) oxalate.

Other tetraalkylammonium hydroxides (R₄ N⁺ OH⁻ and R¹ R² R³ R⁴ N⁺ OH⁻)can be used to prepare the bis(tetraalkylammonium) oxalates. However,bis(tetramethylammonium) oxalate appears to be too insoluble andbis(tetraethylammonium) oxalate forms a very dark-colored mixture.Arylalkyltrimethylammonium compounds (such as benzyltrimethylammoniumand hexadecyltrimethylammonium) can also be used.

The synthesis procedure using methylene chloride was similar to thatdescribed above with methylene bromide using 8.8 g (0.015 mol) ofbis(tetrabutylammonium) oxalate, 25 mL chlorobenzene solvent, and 1.1 mL(1.5 g, 0.017 mol) of methylene chloride. The solution was heated at 85°C. (external oil bath temperature) for 4 days, during which time a whiteprecipitate had formed. The weight of polymer isolated by the sameprocedure described above was 0.22 g.

On evaporation of the solvents from the filtrate and drying of theresidue in vacuo, 8.9 g. of tetrabutylammonium chloride was isolated andcharacterized by its ¹ H NMR spectrum. Tetrabutylammonium chloride canalso be recycled. Bromochloromethane or methylene iodide may be used asthe methylene halide in addition to methylene bromide or methylenechloride.

Other methods of synthesis of PMO were tried, for example, when thepresent inventors tried to synthesize PMO by reacting oxalic acid andmethylene bromide (or methylene chloride) with triethylamine, a methodanalogous to that which was successful in the synthesis of polyglycolide[A. G. Pinkus and R. Subramanyam, J. Polym. Sci., Polym. Chem. Ed., 22,1131 (1984)], polymandelide [A. G. Pinkus, R. Subramanyam, S. L. Clough,and T. C. Lairmore, J. Polym. Sci. Part A. Polym. Chem., 27, 4291(1989)], and polyhydroxymethylbenzoates [A. G. Pinkus, R. Subramanyam,and R. Hariharan, J. Macromol. Sci.--Pure Appl. Chem., A29, 1031(1992)], the reaction did not take place.

Preparation of Poly(alkylene dicarboxylates)

I. Poly(methylene dicarboxylates)

Based on the synthesis of poly(methylene oxalate), dicarboxylic acids(such as terephthalic, isophthalic, dimethylmalonic, malonic, succinic,adipic, fumaric, etc.) are first converted into the correspondingbis(tetraalkylammonium) dicarboxylates by reaction of the dicarboxylicacid HO₂ CRCO₂ H (where R is an aliphatic or aromatic moiety) with twoequivalents of tetraalkylammonium hydroxide:

    2(R.sup.1.sub.4 N.sup.+ OH.sup.-)+HO.sub.2 C--R--CO.sub.2 H→R.sup.1.sub.4 N.sup.+- O.sub.2 C--R--CO.sub.2.sup.-+ NR.sup.1.sub.4 +2H.sub.2 O

The bis(tetraalkylammonium) dicarboxylate is then reacted with analkylene dihalide such as alkylene bromide or alkylene chloride to formthe poly(alkylene dicarboxylate) as described for poly(methyleneoxalate):

    (R.sup.1.sub.4 N.sup.+).sub.2 R(CO.sub.2.sup.-).sub.2 +CH.sub.2 X.sub.2 →R.sup.1.sub.4 N.sup.+ (.sup.- OCORCOOCH.sub.2).sub.n OCORCOO.sup.-+ NR.sup.1.sub.4 +R.sup.1.sub.4 N.sup.+ X.sup.-

X=Cl or Br or I

The preferred tetraalkylammonium hydroxide is tetrabutylammoniumhydroxide and preferred alkylene dihalides are methylene bromide ormethylene chloride.

Synthesis of Poly(methylene terephthalate) by Reaction ofBis(tetrabutylammonium) Terephthalate and Methylene Chloride inChlorobenzene. Methylene chloride (0.10 mL, 0.13 g, 1.5×10⁻³ mol) wasadded to bis(tetrabutylammonium) terephthalate (0.25 g, 3.9×10⁻⁴ mol)under an argon atmosphere followed by 6 mL of chlorobenzene. Thesolution was stirred and heated by a sand bath at 135° C. for 26 hduring which time a precipitate formed. The precipitate was collected bycentrifugation, washed with 4×50 mL of methanol to removetetrabutylammonium bromide, and dried in vacuo 12 hr to obtain 0.046 g,66.5% of polymer; DP by ¹ H NMR end group analysis=107 corresponding toM_(n) =19,000.

Synthesis of Poly(methylene terephthalate) by Reaction ofBis(tetrabutylammonium) Terephthalate and Methylene Bromide inChlorobenzene. The procedure was the same as for the methylene chloridereaction above using bis(tetrabutylammonium) terephthalate (0.24 g,3.7×10⁻⁴ mol), methylene bromide (0.14 mL, 0.34 g, 2.0×10⁻³ mol), andchlorobenzene (6 mL). The solution was heated by an oil bath at 135-138°C. for 27 h during which time a precipitate formed. The precipitate wascollected by centrifugation, washed with 4×50 mL of methanol to removetetrabutylammonium bromide. The precipitate of poly(methyleneterephthalate) was dried in vacuo for 12 h to obtain 0.050 g, 76% yield;DP=450 corresponding to M_(n) =80,000. FIG. 8 shows a ¹ H NMR spectrumand FIG. 9 shows a ¹³ C NMR spectrum of poly(methylene terephthalate)synthesized by this procedure. FIG. 10 shows a ¹ H NMR spectrum of thesame polymer obtained by the reaction of methylene chloride andbis(tetrabutylammonium) terephthalate in DMF. FIG. 11 shows a ¹ H NMRspectrum and FIG. 12 shows a ¹³ C NMR spectrum of the same polymerobtained by the reaction of methylene chloride andbis(tetraethylammonium) terephthalate in DMF.

Synthesis of Poly(methylene terephthalate) by Reaction of MethyleneChloride and Triethylamine in Dimethylformamide. To terephthalic acid(2.2 g, 0.013 mol), were added in succession with stirring:dimethylformamide (DMF) (15 mL), two mole equivalents of triethylamine(3.7 mL, 2.7 g, 0.27 mol), methylene chloride (4.2 mL, 5.6 g, 0.067mol). The solution was stirred under argon and heated by a sand bath at120° C. for 5 days during which time a precipitate had formed. Thereaction mixture was cooled to room temperature, the precipitate wascollected by centrifugation, and washed with 3×50 mL of methanol toremove triethylammonium chloride. The precipitate was dried in vacuo for12 h to obtain 0.78 g, 33% yield; mp, 246-250° C.; DP=160-193corresponding to M_(n) =28,500-33,800.

Synthesis of Poly(methylene terephthalate) by Reaction of MethyleneBromide and Triethylamine in Dimethylformamide. To terephthalic acid(1.1 g, 0.0066 mol) were added in succession with stirring: DMF (15 mL),two equivalents of triethylamine (2.2 mL, 1.6 g, 0.016 mol), andmethylene bromide (0.70 mL, 1.7 g, 0.0099 mol). The solution was stirredunder argon and heated by a sand bath at 120° C. for 24 h during whichtime a precipitate had formed. The reaction mixture was cooled and theprecipitate was collected by centrifugation, and refluxed with 20 mL ofDMF to remove any unreacted acid. The precipitate was then collected bycentrifugation, and washed with 3×50 mL of methanol to removetriethylammonium bromide. The polymeric precipitate was dried in vacuofor 12 h to obtain 0.70 g, 60% yield. The DP from end group analysis was53-65 corresponding to M_(n) =9,400-11,600. FIG. 6 shows a ¹ H NMRspectrum and FIG. 7 shows a ¹³ C NMR spectrum in CDCl₃ /TFAD ofpoly(methylene terephthalate) synthesized by this procedure.

Synthesis of Poly(methylene sebacate) by Reaction ofBis(tetrabutylammonium) Sebacate and Methylene Bromide in Chlorobenzene.Bis(tetrabutylammonium) sebacate (0.941 g, 1.37×10⁻³ mol) was dissolvedin chlorobenzene (10 mL). Methylene bromide (0.11 mL, 0.27 g, 1.37×10⁻³mol) was added and the solution was stirred in a sand bath at 130° C.for 27 h. A white precipitate had formed. The solvent was evaporated ina stream of argon. The solid residue was dissolved in chloroform andextracted 4 times with 5% sodium bicarbonate solution and twice withwater, and then with saturated sodium chloride solution. The chloroformsolution was dried with anhydrous sodium sulfate and evaporated toobtain a solid which was dried in vacuo for 14 h to obtain 0.18 g, 62%yield. ¹ H and ¹³ C NMR in CDCl₃ were obtained. From end group analysis,DP was determined to be 512 corresponding to M_(n) =110,000. FIG. 13shows a ¹ H NMR spectrum and FIG. 14 shows a ¹³ C NMR spectrum ofpoly(methylene sebacate) obtained by this procedure.

II. Poly(ethylene terephthalate) (PET) and Poly(ethylene isophthalate)

Method I: Using triethylamine. Terephthalic acid is reacted with twoequivalents of triethylamine in a suitable solvent to formbis(triethylammonium) terephthalate:

    2Et.sub.3 N+p-HO.sub.2 CC.sub.6 H.sub.4 CO.sub.2 H→Et.sub.3 NH.sup.+- O.sub.2 CC.sub.6 H.sub.4 CO.sub.2.sup.-+ HNEt.sub.3

Bis(triethylammonium) terephthalate is reacted with ethylene chloride(or bromide) in a suitable solvent to form poly(ethylene terephthalate):

    Et.sub.3 NH.sup.+ p-.sup.- O.sub.2 CC.sub.6 H.sub.4 CO.sub.2.sup.-+ HNEt.sub.3 +XCH.sub.2 CH.sub.2 X→Et.sub.3 NH.sup.+ (p-.sup.- O.sub.2 CC.sub.6 H.sub.4 CO.sub.2 CH.sub.2 CH.sub.2).sub.n X+Et.sub.3 NH.sup.+ X.sup.-

Synthesis of Poly(ethylend terephthalate) by Reaction of TerephthalicAcid, Ethylene Bromide, and Triethylamine in Dimethylformamide.Triethylamine (2.9 mL, 2.1 g, 0.021 mol) was added dropwise from asyringe to terephthalic acid (1.7 g, 0.011 mol). DMF (12 mL) was addedand the mixture was stirred 30 min. Ethylene bromide (0.91 mL, 2.26 g,0.013 mol) was added with a syringe. The solution was stirred underargon and heated by a sand bath at 100-110° C. for 28 h during whichtime a precipitate had formed. The reaction mixture was cooled and theprecipitate was collected by filtration, washed several times withanhydrous methanol, and dried to obtain 1.3 g, 62% yield. In a meltingpoint apparatus a sample in a capillary sintered at 130° C. and thenmelted 142-144° C. From end group analysis by ¹ H NMR, DP=27corresponding to M_(n) =5,200. FIG. 15 shows a ¹ H NMR spectrum and FIG.16 shows a ¹³ C NMR spectrum of poly(ethylene terephthalate) obtained bythis procedure.

Synthesis of Poly(ethylene terephthalate) by Reaction of TerephthalicAcid, Ethylene Chloride, and Triethylamine in Dimethylformamide.Triethylamine (2.2 mL, 1.6 g, 0.016 mol) was added dropwise from asyringe to terephthalic acid (2.0 g, 0.0072 mol). DMF (12 mL) was addedand the solution was stirred for 30 min. Ethylene chloride (1.0 mL, 1.3g, 0.015 mol) was added by a syringe. The solution was stirred underargon and heated by a sand bath at 110° C. for 4 days during which timea precipitate formed. The reaction mixture was cooled and theprecipitate was collected by centrifugation, washed several times withanhydrous methanol, and dried; yield, 0.92 g, 58%; DP=62 correspondingto M_(n) =12,000.

Synthesis of Poly(ethylene isophthalate) by Reaction of IsophthalicAcid, Ethylene Bromide, and Triethylamine in Dimethylformamide.Triethylamine (2.0 mL, 1.5 g, 0.014 mol) was added dropwise with asyringe to isophthalic acid (0.91 g, 0.0055 mol). DMF (5 mL) was addedand the solution was stirred for 30 min. Ethylene bromide (0.48 mL, 2.3g, 0.012 mol) was added using a syringe. The solution was stirred underargon and heated by a sand bath at 120° C. for 44 h during which time aprecipitate formed. The mixture was cooled, the precipitate wascollected by centrifugation, washed several times with anhydrousmethanol, and dried, 0.50 g, 50%. DP=23; M_(n) =4,400. FIG. 19 shows a ¹H NMR spectrum and FIG. 20 shows a ¹³ C NMR spectrum of poly(ethyleneisophthalate) obtained by the reaction of ethylene chloride in the aboveprocedure.

Method II: Using bis(tetraethylammonium) terephthalate.Bis(tetraethylammonium) terephthalate is prepared as described above bytitrating tetraethylammonium hydroxide with terephthalic acid.Bis(tetraethylammonium) terephthalate is then reacted with ethylenechloride (or ethylene bromide): ##EQU1##

Synthesis of Poly(ethylene terephthalate) by Reaction of EthyleneBromide and Bis(tetraethylammonium) Terephthalate in Dimethylformamide.Ethylene bromide (0.82 mL, 1.8 g, 0.0095 mol) was added by a syringe tobis(tetraethylammonium) terephthalate (1.7 g, 0.0041 mol) dissolved inDMF (15 mL). The solution was stirred under argon and heated by a sandbath at 125° C. for 16 h during which time a precipitate formed. Thereaction mixture was cooled and the precipitate which formed wascollected by centrifugation, washed with 3×50 mL of anhydrous methanol,and dried in vacuo for 12 h. Yield of polymer=0.35 g, 56%; DP=45corresponding to M_(n) =8,700. FIG. 17 shows a ¹ H NMR spectrum and FIG.18 shows a ¹³ C NMR spectrum of poly(ethylene terephthalate) obtained bythis procedure.

Synthesis of Poly(ethylene terephthalate) by Reaction of EthyleneChloride and Bis(tetraethylammonium) Terephthalate inDimethylformamide). Ethylene chloride (0.36 mL, 1.8 g, 0.0036 mol) wasadded by a syringe to bis(tetraethylammonium) terephthalate (1.4 g,0.0032 mol) dissolved in DMF (15 mL). The solution was stirred underargon and heated by a sand bath at 120° C. for 16 h during which time aprecipitate had formed. The reaction mixture was cooled and theprecipitate was collected by centrifugation, washed with 3×50 mL ofanhydrous methanol, and dried in vacuo for 13 h; yield=0.31 g, 51%;DP=31 corresponding to M_(n) =6,000.

III. Poly(methylene terephthalate-co-ethylene terephthalate)

Copolymers of poly(alkylene dicarboxylates) may be obtained by reactingthe bis(tetraalkylammonium) dicarboxylate salt with a mixture ofalkylene halides such as methylene or ethylene halide. The properties ofthe copolymers can be varied by changing the ratio of alkylene halidesin the mixture. Similarly, a mixture of dicarboxylate salts may yieldcopolymers with desired properties. One skilled in the art wouldunderstand that a copolymer of mixed dicarboxylates would be equivalentto copolymers described herein.

The title copolymers can be prepared by using procedures analogous tothose in Methods I and II. The general method usingbis(tetrabutylammonium) terephthalate is described.Bis(tetrabutylammonium) terephthalate is first prepared fromterephthalic acid and tetrabutylammonium hydroxide by the proceduredescribed above. Bis(tetrabutylammonium) terephthalate is then reactedwith a mixture of methylene chloride (or bromide) and ethylene chloride(or bromide) in an appropriate solvent. The proportions of the twomonomers incorporated into the copolymer are determined by the relativemolar ratios of methylene halide to ethylene halide used. Thus when therelative molar ratios of methylene chloride and ethylene chloride were1:1 (as compared with bis-tetrabutylammonium terephthalate equivalent to2), the relative ratios of CH₂ groups incorporated to CH₂ CH₂ wereapproximately 1:1 based on the relative integrated areas of the twosignals in the ¹ H NMR spectra. This indicates that the relativereactivities of the two monomers under the conditions used is aboutequal. Thus, by reacting the two monomers in other ratios under theseconditions, other compositions can be obtained. For example, a ratio of10:90 of methylene chloride to ethylene chloride respectively would givea copolymer having a copolymer ratio of 10:90 methylene to ethyleneunits. Analogously a 90:10 methylene to ethylene copolymer can beprepared as well as any composition between or outside of these ratios.

Synthesis of Poly(methylene-co-ethylene terephthalate) by Reaction ofBis(tetrabutylammonium) Terephthalate with Methylene Bromide and1,2-Dibromoethane (1:1 Mole Ratio) in Chlorobenzene.Bis(tetrabutylammonium) terephthalate (1.46 g, 2.25×10⁻³ mol) wasdissolved in 15 mL of chlorobenzene and 0.11 mL (0.210 g, 1.13×10⁻³ mol)of methylene bromide and 0.79 mL (0.195 g, 1.13×10⁻³ mol) of1,2-dibromoethane was added. The solution was stirred and heated by anoil bath at 120° C. for 12 h during which a fine white precipitateformed. The mixture was cooled and centrifuged. The precipitate waswashed three times with dry methanol and dried in vacuo; 0.315 g wasobtained. Based on tetrabutylammonium end group analysis and assumingpolymeric units as --OCH₂ OCOC₆ H₄ COOCH₂ CH₂ O-- or 206 mass units, DPwas 631-728 corresponding to M_(n) =117,000-135,000 based on comparisonwith CH₂ and CH₂ CH₂ integrated areas respectively. By comparison of CH₂with CH₂ CH₂ areas, 43 to 57% of CH₂ and CH₂ CH₂ units respectively wereincorporated into the copolymer. The ¹³ C NMR spectrum indicated acopolymer with random distribution of units. On removal of solvent, 1.07g (74%) of tetrabutylammonium bromide was recovered. FIG. 21 shows a ¹ HNMR spectrum and FIG. 22 shows a ¹³ C NMR spectrum of the titlecopolymer obtained by the reaction of methylene bromide and ethylenebromide in the above procedure.

Synthesis of Poly(methylene-co-ethylene terephthalate) by Reaction ofBis(benzyltrimethylammonium) Terephthalate with Methylene Bromide and1,2-Dibromoethane (63:37 Mole Ratio Respectively) in Chlorobenzene. Theprocedure was similar to that used with bis(tetrabutylammonium)terephthalate above using equimolar quantities of methylene bromide(0.12 mL, 0.30 g, 1.7×10⁻³ mol) and 1,2-dibromoethane (0.15 mL, 0.19 g,1.0×10⁻³ mol), bis(benzyltrimethylammonium) terephthalate (0.688 g,2.10×10⁻³ mol), in chlorobenzene solvent (20 mL) at 120° C. for 12 h.The copolymer was isolated according to the same procedure as above(0.0162 g). ¹ H and ¹³ C spectra were obtained using 0.0031 g ofcopolymer in 0.57 g (95%) of CDCl₃ and 0.031 g (5%) of TFAD by weight.From the integration of CH₂ relative to CH₂ CH₂ signals, the CH₂ groupwas incorporated to the extent of 21% compared to 79% of the CH₂ CH₂group and DP=207 corresponding to M_(n) =38,000. FIG. 23 shows a ¹ H NMRspectrum of the title copolymer obtained by this procedure.

Synthesis of Poly(methylene terephthalate-co-ethylene terephthalate)(90:10) by Reaction of Bis(tetrabutylammonium) Terephthalate withMethylene Bromide and 1,2-Dichloroethane (90:10 Mole Ratio Respectively)in Chlorobenzene. The procedure was the same as that described above forthe 50:50 copolymer using methylene bromide (0.114 mL, 0.282 g.,1.62×10⁻³ mol, 90%), 1,2-dibromoethane (0.016 mL, 0.056 g, 1.8×10⁻⁴ mol,10%), bis(tetrabutylammonium) terephthalate (1.16 g, 1.79×10⁻³ mol).Weight of polymer obtained=0.209 g, 65%. ¹ H and ¹³ C NMR spectra weretaken in CDCl₃ /TFA. The CH₂ to CH₂ CH₂ incorporation into the copolymerwas 80:20 respectively indicating greater reactivity of1,2-dichloroethane. Based on end-group analysis from the ¹ H NMRspectrum, the DP was 327 from integration of CH₂ and CH₂ CH₂ groups and363 based on the aromatic hydrogens. These correspond to M_(n) values of59,000 and 66,000 respectively making the same assumptions as above.

Synthesis of Poly(methylene-co-ethylene terephthalate) by Reaction ofBis(tetrabutylammonium) Terephthalate with Methylene Bromide and1,2-Dichloroethane (17:83 Mole Ratio Respectively) in Chlorobenzene. Thesame procedure as above was carried out using bis(tetrabutylammonium)terephthalate (1.57 g, 2.42×10⁻³ mol), ethylene bromide (0.374 g, 0.18mL, 2.0×10⁻³ mol), and methylene bromide (0.059 g, 0.020 mL, 3.4×10⁻⁴mol). The yield of polymer was 0.291 g, 59%. The incorporation of CH₂and CH₂ CH₂ units were 12:88 respectively indicating the greaterreactivity of 1,2-dichloroethane. The DP of the copolymer was 609corresponding to M_(n) =125,500 making the same assumption as above.FIG. 24 shows a ¹ H NMR spectrum and FIG. 25 shows a ¹³ C NMR spectrumof the title copolymer obtained by this procedure.

Synthesis of Poly(methylene-co-ethylene terephthalate) by Reaction ofTerephthalic Acid with Methylene Bromide and Ethylene Bromide (1:1 MoleRatio) and Triethylamine in Dimethylformamide. Triethylamine (2.2 mL,1.6 g, 0.016 mol) was added dropwise from a syringe to terephthalic acid(1.3 g, 0.0078 mol). DMF (25 mL) was added and the mixture was stirredfor 0.5 h. Ethylene bromide (0.33 mL, 0.72 g, 0.0039 mol) and methylenebromide (0.27 mL, 0.67 g, 0.0039 mol) were added with a syringe. Thesolution was stirred under argon and heated by a sand bath at 100° C.for 10 h during which time a precipitate formed. The mixture was cooledand the precipitate was collected by centrifugation, washed severaltimes with anhydrous methanol, and dried for 23 h in vacuo to obtain0.95 g, 59% yield. A ¹ H nmr spectrum was obtained by dissolving 0.026g, (3.6% by wt.) of polymer in 0.67 g (89% by wt.) CDCl₃ and 0.05 g (6%by wt.) of trifluoroacetic acid-d. DP=63; M_(n) =12,000 (assumingmolecular weight of one unit as 222 mass units corresponding to C₁₁ H₁₀O₅). By comparison of CH₂ with CH₂ CH₂ areas, 36 to 64% of CH₂ and CH₂CH₂ units respectively were incorporated into the copolymer. The ¹ H NMRshowed δ (ppm) signals at 4.78, CH₂ CH₂ ; 6:30, CH₂ ; 8.13-8.20, arom.FIG. 26 shows a ¹ H NMR spectrum and FIG. 27 shows a ¹³ C NMR spectrumof the title copolymer obtained by the reaction of ethylene chloride inplace of ethylene bromide in the above procedure.

A significant value for applications of the title copolymers is that theproperties of the copolymers can be varied between those of theconstituent homopolymers by changing the molar ratios of the feedmonomers as described.

IV. Poly[(methylene dicarboxylates)-co-(ethylene dicarboxylates)]

These copolymers are prepared by reactions of bis(tetrabutylammonium)dicarboxylates with varying proportions of methylene chlorides (orbromides) and ethylene chloride (or bromide): ##EQU2##

Synthesis of Poly(methylene oxalate-co-ethylene oxalate) by Reaction ofMethylene Bromide and Ethylene Bromide (1:1 Mole Ratio) withBis(tetrabutylammonium oxalate) in Chlorobenzene. Tobis(tetrabutylammonium) oxalate (8.3 g, 0.015 mol), 15 mL ofchlorobenzene was added with stirring followed by 0.5 mL (1.3 g, 0.0073mol) of methylene bromide and 0.6 mL (1.1 g, 0.0073 mol) of ethylenebromide. The solution was stirred under argon and heated by an oil bathat 120° C. for 48 h during which time a precipitate formed. Aftercooling to room temperature, the precipitate was collected bycentrifugation and washed with 4×25 mL of anhydrous methanol. Thepolymer was dried in vacuo for 12 h to obtain 0.17 g of polymer. Thepolymer was insoluble in common organic solvents. The polymer did notmelt to 300° C. and is nonflammable. The DSC of the polymer showed apattern similar to that of poly(methylene oxalate) and starteddecomposing at 710° K. FIG. 28 shows an IR spectrum of the titlecopolymer obtained by this procedure.

V. Poly(R' dicarboxylates)

Bis(tetrabutylammonium) dicarboxylates prepared as described above arereacted with a dihalide, X--R'--X where X=Br or Cl and R'=--CH₂--Ar--CH₂ -- or --CH₂ CH═CHCH₂ -- where Ar=an aromatic group such as1,4- or 1,3-C₆ H₄. The main point is that the Ar (or vinyl) group actsto make the halogen more reactive.

Synthesis of Poly(p-xylene terephthalate) by Reaction ofα,α'-Dibromo-p-xylene with Terephthalic Acid and Triethylamine inDimethylformamide. Triethylamine (2.3 mL, 1.6 g, 0.016 mol) was addeddropwise from a syringe to terephthalic acid (1.1 g, 0.0067 mol). DMF(25 mL) was added and the mixture was stirred for 0.5 h.α,α'-Dibromo-p-xylene (1.8 g, 0.0068 mol) was added and the solution wasstirred under argon and heated by a sand bath at 120° C. for 27 h duringwhich time a precipitate had formed. The reaction mixture was cooled andthe precipitate was collected by centrifugation, washed several timeswith anhydrous methanol, and dried for 14 h in vacuo to obtain 0.10 g,55% yield; mp=255-260° C.; DP=81; M_(n) =21,700. FIG. 29 shows a ¹ H NMRspectrum and FIG. 30 shows a ¹³ C NMR spectrum of the title copolymerobtained by this procedure.

Synthesis of Poly(p-xylene terephthalate) by Reaction ofα,α'-Dichloro-p-xylene with Terephthalic Acid and Triethylamine inDimethylformamide. Triethylamine (3.4 mL, 2.4 g, 0.024 mol) was addeddropwise from a syringe to terephthalic acid (1.7 g, 0.010 mol). DMF (32mL) was added and the mixture was stirred for 0.5 h.α,α'-Dichloro-p-xylene (1.9 g, 0.011 mol) was added. The solution wasstirred under argon and heated by a sand bath at 120° C. for 38 h duringwhich time a precipitate formed. The reaction mixture was cooled and theprecipitate was collected by centrifugation, washed several times withanhydrous methanol, and dried for 15 h in vacuo to obtain 1.4 g, 51%yield; DP=50; M_(n) =13,500.

Synthesis of Poly(m-xylene terephthalate) by Reaction ofα,α'-Dibromo-m-xylene with Bis(tetraethylammonium) Terephthalic inDimethylformamide. To 0.66 g (0.0016 mol) of bis(tetraethylammonium)terephthalate 15 mL of DMF and 0.411 g (0.0016 mol) ofα,α'-dibromo-m-xylene were added. The solution was stirred under argonand heated by a sand bath at 120° C. for 48 h. The reaction mixture wascooled and poured into ice water. The precipitate which formed wascollected by filtration and washed twice with 20 mL of water. Theprecipitate was then triturated with n-heptane to remove unreactedα,α'-dibromo-m-xylene. The polymer was filtered and dried in vacuo for10 h to obtain 0.20 g, 47% yield; DP=627 corresponding to M_(n)=168,000. The double bond in this polymer could be the site ofcrosslinking. FIG. 31 shows a ¹ H NMR spectrum and FIG. 32 shows a ¹³ CNMR spectrum of the title copolymer obtained by the reaction ofα,α'-dichloro-m-xylene in place of the bromo derivative in the aboveprocedure.

Synthesis of Poly(2-E-butenyl terephthalate) by Reaction of1,4-Dibromo-2-E-butene and Bis(tetraethylammonium) Terephthalate inDimethylformamide. Bis(tetraethylammonium) terephthalate (2.20 g,5.12×10⁻³ mol) was added to dimethylformamide (15 mL). (The salt was notsoluble in hot chlorobenzene.) 1,4-Dibromo-2-E-butene (1.10 g, 5.12×10⁻³was added and the solution heated by an oil bath at 130° C. for 28 hduring which time a precipitate formed. After cooling the precipitatewas collected by centrifugation, washed 4 times with anhydrous methanol,and dried in vacuo to obtain 1.49 g, 52% yield. FIG. 33 shows a ¹ H NMRspectrum and FIG. 34 shows a ¹³ C NMR spectrum of the title polymerobtained by this procedure.

Synthesis of Poly(2-E-butenyl terephthalate) [Poly(oxy-2-butene-1,4-diyloxycarbonyl-1,4-phenylenecarbonyl)] by Reaction of1,4-Dibromo-2-E-butene, Terephthalic Acid and Triethylamine in DMF.Triethylamine (0.36 mL, 0.27 g, 0.0027 mol) was added dropwise from asyringe to terephthalic acid (0.22 g, 0.0013 mol). DMF (10 mL) was addedand the mixture was stirred for 0.5 h. 1,4-Dibromo-2-E-butene (0.27 g,0.0013 mol) was added. The solution was stirred under argon for 30 min.A dense white precipitate was formed which dissolved on heating. Thesolution was heated by a sand bath at 120° C. for 8 h during which timea precipitate had formed. The mixture was cooled and the precipitate wascollected by centrifugation, washed several times with anhydrousmethanol, and dried for 14 h in vacuo to obtain 0.17 g, 57% yield. Fromend group analysis, DP=5 corresponding to M_(n) =1,100. FIG. 35 shows a¹ H NMR spectrum and FIG. 36 shows a ¹³ C NMR spectrum of the titlepolymer by this procedure.

Synthesis of Poly(methylene-co-2-butenyl terephthalate) 53:47 byReaction of Methylene Bromide, 1,4-Dibromo-2-butene, andBis(tetraethylammonium) Terephthalate in Dimethylformamide. To 1.3 g(0.0031 mol) of bis(tetraethylammonium) terephthalate, 0.29 g (0.0017mol) of methylene bromide, 0.32 g (0.0015 mol) of 1,4-dibromo-2-butene,and 18 mL of DMF were added. The mixture was stirred for 12 h at ambienttemperature. A white precipitate was formed after 15 min. The mixturewas then heated to 125° C. for 24 h with a sand bath. The mixture wascooled and the precipitate was collected by centrifugation and washedwith anhydrous methanol three times with 30 mL each. The polymer wasdried under vacuum for 12 h and weighed, 0.30 g (57% yield assuming themass of the polymer units to be 168. A ¹ H NMR spectrum of the polymerwas obtained by dissolving 13 mg (0.16% by weight of total mixture) ofthe polymer in 0.78 g (99% by weight) of CDCl₃ and 0.0024 g (0.34% byweight) of TFA-d mixture. The incorporation of CH₂ and CH₂ --CH═CH--CH₂units into the polymer were 60:40 respectively. The DP of the copolymerwas 163 corresponding to M_(n) =32,000. FIG. 39 shows a ¹ H NMR spectrumand FIG. 40 shows a ¹³ C NMR spectrum of the title copolymer obtained bythis procedure.

Synthesis of Poly(methylene-co-p-xylene terephthalate) by Reaction ofMethylene Bromide and α,α'-dibromo-p-xylene (1:1 mole Ratio) withBis(tetraethylammonium) Terephthalic in Dimethylformamide. To 2.5 g(0.0059 mol) of bis(tetraethylammonium) terephthalate 20 mL of DMF and0.77 g (0.0029 mol) of α,α'-dibromo-p-xylene were added followed by 0.21mL (0.53 g, 0.0030 mol) of methylene bromide. The solution was stirredunder argon and heated by a sand bath at 120° C. for 28 h during whichtime a precipitate had formed. The reaction mixture was cooled, theprecipitate was collected by centrifugation, washed with 4×50 mL ofanhydrous methanol and dried in vacuo for 15 h. Yield of the polymer was0.90 g, 50%; DP=237 corresponding to M_(n) =53,000. By comparison of CH₂and p-CH₂ C₆ H₄ CH₂ areas 48 to 52% of CH₂ and p-CH₂ C₆ H₄ CH₂ unitsrespectively were incorporated into the copolymer. The spectra indicateda copolymer with random distribution of units. FIG. 37 shows a ¹ H NMRspectrum and FIG. 38 shows a ¹³ C NMR spectrum of the title copolymerobtained by this procedure.

VI. Bis-(Tetraalkylammonium) Dicarboxylates

Bis(tetrabutylammonium) or bis(triethylammonium) dicarboxylates areprepared from the dicarboxylates described above. These are reacted withethylene chloride (or ethylene bromide) as described above for thereaction with bis(tetrabutylammonium) or bis(triethylammonium)terephthalate: ##EQU3##

General Procedure. A sample of diacid was weighed and dissolved in anappropriate solvent. It was titrated under an inert atmosphere (forexample, argon) with two molar equivalents of a tetraalkylammoniumhydroxide (the alkyl groups can be the same or different: R¹ R² R³ R⁴)dissolved in the same (or a compatible solvent) to an endpoint. Anyprecipitates were removed at this point. The solvent was removed fromthe filtrate by rotary vacuum evaporation to obtain thebis(tetraalkylammonium) dicarboxylate salt which was dried in vacuo,weighed, and characterized by spectral means.

Synthesis of Bis(tetrabutylammonium) Terephthalate. Terephthalic acid(0.439 g., 2.64×10⁻³ mol) (dried in vacuo at 60° C.) partially dissolvedin 10 mL of methanol was titrated under an argon atmosphere with 5.3 mL(1.4 g, 5.3×10⁻³ mol) of tetrabutylammonium hydroxide solution (1 M) inmethanol. A fine white precipitate which had formed was removed bycentrifugation, washed with methanol, and dried in vacuo, weighed (0.037g) and discarded. The solvent was removed from the filtrate by rotaryvacuum evaporation and the salt residue was dried in vacuo at 60° C. for18 h to obtain 1.60 g (92%) of product. NMR spectra of the salt wereobtained in CDCl₃, FIGS. 41 and 42.

Synthesis of Bis(benzyltrimethylammonium) Terephthalate. The procedurewas the same as described above for bis(tetrabutylammonium)terephthalate using 0.277 g (1.67×10⁻³ mol) of terephthalic acid andbenzyltrimethylammonium hydroxide (3.4 mL, 0.57 g, 3.6×10⁻³ mol) (40% byweight in methanol). The yield of salt obtained after removal of solventwas 0.688 g, 88%. ¹ H and ¹³ C NMR spectra (FIGS. 47 and 48) of the saltin D₂ O were obtained and are in accord with the expected structure.

Synthesis of Bis(tetrabutylammonium) Sebacate. The procedure used wasthe same as described above by titration of sebacic acid (0.814 g,4.02×10⁻³ mol) with 1 M tetrabutylammonium hydroxide solution inmethanol. After removal of solvent, a quantitative yield (2.75 g) ofsalt was obtained. FIG. 45 shows a ¹ H NMR spectrum and FIG. 46 shows a¹³ C NMR spectrum of the salt in CDCl₃.

Synthesis of Bis(tetraethylammonium) Terephthalate.

Terephthalic acid (2.5 g, 0.015 mol) was titrated with a 40% aqueoussolution of tetraethylammonium hydroxide (11.3 mL). The solvent wasevaporated to obtain a hard residue which was dissolved in methanol. Themethanol was evaporated to obtain 5.8 g, 92% yield of salt. FIG. 43shows a ¹ H NMR spectrum and FIG. 44 shows a ¹³ C NMR spectrum of thesalt in DMSO-d₆.

APPLICATIONS

All of the above polymers can form fibers.

To obtain information on melting points (Tm) and high temperaturestability, differential scanning calorimetry measurements were made. Theresults are presented in Table 1.

                  TABLE 1                                                         ______________________________________                                        DSC THERMOGRAM OF THE POLYMERS                                                                             Temp. of                                                            Temp. of  Gradual                                                             Sharp     Decom-                                           Sample             Endotherm position                                         ______________________________________                                        Poly(methylene terephthalate)                                                                    --        377° C.                                   Poly(ethylene terephthalate)                                                                     250° C.                                                                          305° C.                                   Poly(1,4-but-2-ene terephthalate)                                                                332° C.                                                                          410° C.                                   Poly(p-xylene terephthalate)                                                                     357° C.                                                                          397° C.                                   Poly(methylene terephthalate-co-                                                                 --        340° C.                                   ethylene terephthalate) (43:57)                                               Poly(methylene terephthalate-co-                                                                 327° C.                                                                          360° C.                                   ethylene terephthalate (80:20)                                                Poly(methylene terephthalate-co-                                                                 279° C.                                                                          307° C.                                   ethylene terephthalate) (12:88)                                               Poly(methylene terephthalate-co-                                                                 290° C.                                                                          390° C.                                   xylene terephthalate) (48:52)                                                 Poly(methylene terephthalate-co-                                                                 392° C.                                                                          405° C.                                   1,4-but-2-ene terephthalate)                                                  (60:40)                                                                       ______________________________________                                    

T_(m) values ranged from about 250° C. to about 392° C. forpoly(methylene terephthalate-co-1,4-but-2-ene terephthalate). Theintroduction of methylene units into copolymers with poly(ethyleneterephthalate) increases the value of Tm as well as the stability todecomposition.

Tables 2 and 3 present a comparison of the mechanical properties of thepolyesters.

                  TABLE 2                                                         ______________________________________                                        A COMPARISON OF MECHANICAL PROPERTIES                                         OF THE POLYESTERS                                                                                         Binds        Binds                                           Pulls   Sticks to                                                                              Glass Sticks to                                                                            Glass to                             Sample     Fibers  Glass    to Glass                                                                            Metals Metals                               ______________________________________                                        Poly(methylene                                                                           Yes     No       No    No     No                                   terephthalate)                                                                Poly(ethylene                                                                            Yes     No       No    No     No                                   terephthalate)                                                                Poly(1,4-but-2-ene                                                                       Yes     No       No    No     No                                   terephthalate)                                                                Poly(p-xylene                                                                            Yes     No       No    No     No                                   terephthalate)                                                                ______________________________________                                    

                  TABLE 3                                                         ______________________________________                                        A COMPARISON OF MECHANICAL PROPERTIES                                         OF THE POLYESTERS                                                                                         Binds        Binds                                           Pulls   Sticks to                                                                              Glass Sticks to                                                                            Glass to                             Sample     Fibers  Glass    to Glass                                                                            Metals Metals                               ______________________________________                                        Poly(methylene                                                                           Yes     Yes      Yes   Yes    Yes                                  terephthalate-co-                                                             ethylene                                                                      terephthalate)                                                                (43:57)                                                                       Poly(methylene                                                                           Yes     Yes      Yes   Yes    Yes                                  terephthalate)-co-                                                            ethylene                                                                      terephthalate)                                                                (80:20)                                                                       Poly(methylene                                                                           Yes     Yes      Yes   Yes    No                                   terephthalate)-co-                                                            ethylene                                                                      terephthalate)                                                                (12:88)                                                                       Poly(methylene                                                                           Yes     Yes      Yes   Yes    Yes                                  terephthalate)-co-p-                                                          xylene                                                                        terephthalate)                                                                (48:52)                                                                       Poly(methylene                                                                           Yes     Yes      Yes   Yes    Yes                                  terephthalate)-co-                                                            1,4-but-2-ene                                                                 terephthalate)                                                                (60:40)                                                                       ______________________________________                                    

Poly(methylene terephthalate), poly(ethylene terephthalate),poly(1,4-but-2-ene terephthalate), and poly(p-xylene terephthalate) whenmelted, do not adhere to glass or metals. The methylene-containingcopolymers, in general, however, adhere to glass and metals (includingaluminum, iron, and copper). Some of these are clear films, as forexample poly(methylene-co-ethylene terephthalate). This property couldbe of use in the protection of metals or glass from corrosion orscratching. In addition, glass can be bound to glass or to metal ormetal to metal seals can be made.

Tables 4 and 5 present a determination of the number average molecularweight of polyglycolide and a poly(methylene terephthalate-co-ethyleneterephthalate) by end group analysis.

                  TABLE 4                                                         ______________________________________                                        Determination of M.sub.n of Polyglycolide By End Group Analysis.sup.1                                Integration of                                                                           Integration Per                             Sample     Peak Position (δ)                                                                   the Peak   Proton                                      ______________________________________                                        CH.sub.2 -COO.sup.-                                                                    4.9       103        52                                                       (CH.sub.3 CH.sub.2).sub.3 NH.sup.+                                                      1.38-1.41(t)                                                                             9 1                                                      (CH.sub.3 CH.sub.2).sub.3 NH.sup.+                                                      3.55-3.61(q)                                                                             6 1                                             ______________________________________                                         .sup.1 End group is triethylammonium                                          DP = Integration per proton of CH.sub.2 repeating unit/Integration per        proton of the end group                                                       DP = 52/1 = 52                                                                M.sub.n = DP × M.Wt. one repeating unit = 52 × 58 = 3,000    

                  TABLE 5                                                         ______________________________________                                        Determination of M.sub.n of a Poly(methylene                                  terephthalate-co-ethylene terephthalate) By End Group Analysis.sup.1                                 Integration of                                                                           Integration Per                             Sample     Peak Position (δ)                                                                   the Peak   Proton                                      ______________________________________                                        p-OOCC.sub.6 H.sub.4 COO.sup.-                                                         8.13-8.20 334        84                                                       CH.sub.2 CH.sub.2 -                                                                     4.78       163 41                                                   CH.sub.2 -                                                                              6.30       46.6 23                                                  (CH.sub.3 CH.sub.2).sub.3 NH.sup.+ -                                                    1.42-1.47(t)                                                                             9 1                                                      (CH.sub.3 CH.sub.2).sub.3 NH.sup.+ -                                                    4.43-4.50(q)                                                                             6 1                                             ______________________________________                                         .sup.1 End group is triethylammonium                                          The ratio of methylene to ethylene units is 36:64                             M.Wt. of one unit of poly(methylene terephthalate) = 178                      M.Wt. of one unit of poly(ethylene terephthalate) = 192                       Therefore, the M.Wt. of one unit of copolymer = (178 × 0.36) + (192     × 0.64) = 187                                                           By similar calculation as shown for homopolymer DP = 64 to 84; M.sub.n =      12,000 to 16,000.                                                        

Poly(methylene malonate), poly(methylene dimethylmalonate), andpoly(methylene fumarate) have also been made but the products obtainedso far are oils for which uses have not as yet been found. Thecorresponding bis(tetrabutylammonium) carboxylates have also been made.

The pertinent parts of the following references are incorporated byreference herein for the reasons cited.

REFERENCES

Carothers et al., J. Am. Chem. Soc., 52:3292 (1930).

Carothers, U.S. Pat. No. 2,071,251.

Carothers, U.S. Pat. No. 2,071,250.

Chem. Abst., 99:21307 (1983).

Cimecioglu et al., Makromol. Chem. Rapid Commun., 10:319 (1989).

Cimecioglu et al., Journal of Polymer Science: Part A: PolymerChemistry, 26:2129-2139 (1988).

Cimecioglu et al., Journal of Polymer Science: Part A: PolymerChemistry, 30:313-321 (1992).

East and Morshed, Polymer, 23:168-170 and 1555-1557 (1982).

Ellis, U.S. Pat. No. 2,111,762 (1938).

Gordon et al., Polym. Prepr. Am. Chem. Soc., Div. Polym. Chem., 31, 507(1990).

JP Appl. 82/UT24503, Feb. 23, 1982.

Kielkiewicz et al., Polimery (Warsaw), 27:374 (1982); Chem. Abst.,99:38837 (1982).

Makarevich et al., Zh. Prikl. Spektrosk. 50:65 (1989) Chem. Abst.,110:201792, (1989).

Nishikubo et al., Polym. J., 22:1043 (1990).

Otsuka Chemical Co., Ltd., Jpn. Pat. 582154430, December 1983, Chem.Abst., 100:175926 (1984).

Pinkus et al., J. Polym. Sci., Polym. Chem. Ed., 22:1131 (1984).

Pinkus et al., J. Polym. Sci. Part A. Polym. Chem., 27:4291 (1989).

Pinkus et al., J. Macromol. Sci.--Pure Appl. Chem., A29:1031 (1992).

Piraner et al., Makromol. Chem., 193:681 (1992).

Rokicki et al. Polimery (Warsaw), 1982, 27:374; Chem Abst. 99:38837(1982)

Shalaby et al., U.S. Pat. No. 4,141,087 (1979).

Shiba, H., DE 3,306,089, Sep. 1, 1983.

Thibeault et al., J. Polym. Sci., Pt. A: Polym. Chem., 28, 1361 (1990).

Applicant understands that one of skill in the art may substituteobvious equivalents of the following claimed chemical structures andmethods.

What is claimed is:
 1. A method for preparing a bis(tetraalkylammonium)dicarboxylate salt, comprising:reacting a dicarboxylic acid withtetraalkyl ammonium hydroxide to form a bis(tetraalkylammonium)dicarboxylate salt.
 2. The method of claim 1 where the dicarboxylic acidis terephthalic acid or sebacic acid.
 3. The method of claim 1 where thetetraalkyl ammonium hydroxide is tetrabutyl-, tetraethyl- orbenzyltrimethylammonium hydroxide.